Chemistry and Technology of Fuels and Oils, Vol. 40, No.

4, 2004

TECHNOLOGY

REMOVAL OF AROMATIC HYDROCARBONS FROM REFORMING NAPHTHA.

COMBINED EXTRACTION – EXTRACTIVE-AZEOTROPIC DISTILLATION
PROCESS

A. A. Gaile, G. D. Zalishchevskii, N. N. Gafur, L. V. Semenov, UDC 66.061

O. M. Varshavskii, N. P. Fedyanin, and L. L. Koldobskaya

Separation of C 6-C 9 aromatic hydrocarbons from naphtha cut reformate by extraction with sulfolane
followed by extractive/azeotropic distillation of the extract phase with sulfolane and ethanol.
For mass ratios of sulfolane to feedstock of 1.6:1 and 0.28:1 in the stages of extraction and
extractive-azeotropic distillation and a ratio of ethanol to feedstock of 0.032:1, raffinate was obtained
with a yield of 65 wt. %, which satisfies the long-term environmental requirements for gasoline and
benzene, toluene, and C 8 and C 9 aromatic hydrocarbons with a yield of 89, 77, 69, and 24 wt. %. Key
words: reformate, aromatic hydrocarbons, extraction, extractive distillation, sulfolane, ethanol.

According to the European specifications Euro-3, in effect since 2001, the total aromatic hydrocarbon
content in automotive gasoline must be a maximum of 42 vol. %, including a maximum of 1 vol. % for benzene.
The Euro-4 program, targeted for introduction in 2005, provides for a further decrease in the total aromatic
hydrocarbon content in gasoline to 30 vol. % [1].

Table 1
Content (wt. %) in reformate

Hydrocarbons from unit

combined
LG-35-8/300B L-35-11/600 LCh-35-11/1000

Paraffins + naphthenes 59.5 36.7 33.5 44.4

Aromatics 40.5 63.3 66.5 55.6

benzene 16.5 0.4 6.3 6.9
toluene 22 16.2 31.5 22.5
xylenes 2 46.3 11.9 17.2
С9 – 0.4 16.8 9

____________________________________________________________________________________________________
St. Petersburg State Technological Institute. Kirishinefteorgsintez Industrial Association. Translated
from Khimiya i Tekhnologiya Topliv i Masel, No. 4, pp. 11 – 14, July – August, 2004.

0009-3092/04/4004–0215 ©2004 Springer Science+Business Media, Inc. 215

 Table 2

Extractant γ g0 / γ b0 γ b0γ ch0 γ Ar

0
γ ch0 / γ Ar
0
Literature

Sulfolane 17.2 21.8 7.35* 3 [15]

Triethylene glycol 10.5 16.9 9.97* 1.7 [15]
Tetraethylene glycol 10 13.7 6.9** 2 [16]

Notes. * For C 9 hydrocarbon – pseudocumene.

** Calculated with the activity coefficient of benzene γ b0 and selectivity of tetraethylene glycol based
on molecular weights.

Table 3

Experiment
Process parameters
1 2 3 4

Number of theoretical stages 7 7 5 5

Temperature in extractor, °C
in upper part 50 50 50 50
in lower part 50 30 50 50
Extractant:feedstock (wt.) 5:1 1.6:1 3:1 2:1
Water content in sulfolane, wt. % 0.05 2 0.05 0.2

The USA has even stiffer requirements for this index – a maximum of 25 vol. %, and 22 vol. % in the state
of California, including a maximum of 1 and 0.8 vol. % for benzene [2]. Noncompliance with these restrictions
will will cause important carbon formation in engines and elevated emission of unburned toxic aromatic
hydrocarbons, especially carcinogenic benzene, with the exhaust gases.
Sale of gasoline with improved environmental properties will take effect in Russia in 2003 for cities with
high traffic density: maximum total aromatic hydrocarbon content of 45 vol. %, including 1-3 vol. % benzene,
under 0.03 wt. % sulfur, and 20 vol. % olefins [3].
The high aromatic hydrocarbon content in domestic high-octane gasolines is due to the existing oil
refining structure in the country. Reformate with an aromatic hydrocarbon content of up to 65-68 vol. %, including
up to 8 vol. % benzene, is the basic component of Russian gasolines. The proportion of reformate in the Russian
gasoline pool is 54.3 wt. %, while it is 34.6 wt. % in the USA and 46.9 wt. % in Western Europe [1].
Increasing the proportion of other high-octane components in domestic automotive
gasolines – isomerizates, alkylates, oxygenates – is held back by high production costs, which
are 2.26 and 3.57 times higher for alkylates and diisopropyl ether than for reformates [4].
In the near future, Russia and even the Western European countries will not approach the USA with
respect to the structure of oil refining and the composition of the gasoline pool. To satisfy the EU environmental
requirements for gasolines from reformates, it is necessary to extract excess benzene and other aromatic
hydrocarbons.

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 It is suggested that in 2005, for predicted consumption of gasoline in the EU equal to 150 million
tons/year, 8 million tons/year of benzene, toluene, and xylenes will appear on the market in addition to the existing
10 million tons/year of aromatic hydrocarbons [5]. The necessity of reducing the benzene content in gasoline also
requires separation by sulfolane extraction [6] or extractive distillation with N-formylmorpholine in Japan as
well [7].
Extraction of aromatic hydrocarbons from reformates of narrow naphtha cuts, 62-105, 105-140, and 62-140°C,
has been thoroughly investigated [8-11]. This process has not been used or sufficiently investigated for reformates of
the wide 62-200°C naphtha cut.
We developed a combined method for separation of excess aromatic hydrocarbons from naphtha cut
reformate by extraction followed by extractive-azeotropic distillation.
The feedstock was combined reformate from LG-35-8/300B, L-35-11/600, and LCh-35-11/1000 units at
Kirishinefteorgsintez Industrial Association in the mass ratio of 19.4:27.6:53 corresponding to their real output.
The hydrocarbon composition of the reformates is reported in Table 1.
The extractant should have low selectivity for molecular weights, characterized by a ratio of
limiting n-paraffin activity coefficients γ i0 – octane and heptane or heptane and hexane in a solvent – for effective
extraction of aromatic hydrocarbons from wide-distilling crude oil cuts.
The molecular weight selectivity values for 683 solvents and the group selectivity with respect to aromatic
hydrocarbons in separation from mixtures of paraffins, naphthenes, and olefins calculated with the activity
coefficients γ i0 of hydrocarbons in [12, 13] are reported in [14].
However, for solving the problem posed, such existing comparatively low-boiling extractants as furfural,
phenol, dimethyl sulfoxide, N-methylpyrrolidone, ethylene glycol, and also higher boiling N-formylmorpholine
and diethylene glycol, are not very suitable. All of these solvents form azeotropic mixtures with the hydrocarbons
in the feedstock and this makes it difficult to regenerate them. There is thus a narrow choice of comparatively
high-boiling selective solvents tested in industry as extractants: sulfolane, tri- and tetraethylene glycol.
Low-boiling C 6 naphthenes (methylcyclopentane or cyclohexane, which have close activity coefficients
in polar solvents) and high-boiling C 9 aromatic hydrocarbons are the key, most difficult to separate pairs of
components. The limiting activity coefficients of the key hydrocarbons in extractants at 70°C and the selectivity
of the latter with respect to the key pair ( γ ch / γ Ar ) and the cyclohexane–benzene system ( γ ch / γ b b ) are reported
0 0 0 0

in Table 2.
As the data show, the selectivity of the solvents with respect to the key pair of components is 5-6 times
lower than the group selectivity for the hexane–benzene system ( γ h / γ b ). This is also the cause of the decrease
0 0

in the efficiency of extraction of aromatic hydrocarbons from cuts with wide distillation limits in comparison to the
efficiency of separation of hydrocarbons with the same number of carbon atoms in the molecules.
In comparison to tri- and tetraethylene glycols, sulfolane retains 1.5-1.8 times higher selectivity with
respect to the key pair of components due to its higher group selectivity combined with lower molecular weight
selectivity [17]. For this reason, sulfolane has also been selected as an extractant for C 6-C 9 aromatic hydrocarbons.
The conditions in Experiment 1 were set to ensure as complete extraction as possible of not only benzene
but also other aromatic hydrocarbons (Table 3). Experiment 2 was conducted to extract most of the benzene and
to a lesser degree its homologs and obtain a high yield of raffinate that satisfies the requirements for a component
of environmentally clean automotive gasoline.

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 Table 4
Degree of
extraction of
Indexes Raffinate Extract aromatic
hydrocarbons, wt.
%
1 2 3 4

Experiment 1
Yield, wt. % 15.6 84.4 –
Hydrocarbon composition, wt. %

saturated >99.9 34.1 –

aromatic <0.1 65.9 ~100
benzene – 8.2 100
toluene – 26.5 100
C8 – 20.5 100
C9 <0.1 10.7 ~100

Experiment 2
Yield, wt. % 60 40 –
Hydrocarbon composition, wt. %
saturated 70.5 5.3 –
aromatic 29.5 94.7 68
benzene 0.5 16.5 95
toluene 8.7 43.2 77
C8 9 29.5 69
C9 11.3 5.5 24

Experiment 3
Yield, wt. % 28.6 71.4 –
Hydrocarbon composition, wt. %

saturated 93.92 24.5 –

aromatic 6.08 75.5 96.96
benzene 0.03 9.7 99.9
toluene 0.61 31.3 99.3
C8 2.57 23.1 95.9
C9 2.87 11.4 90.4

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 Table 4 (continued)

1 2 3 4
Experiment 4

Yield, wt. % 36 64 –

Hydrocarbon composition, wt. %

saturated 84.1 22.2 –

aromatic 15.9 77.8 89.5
benzene 0.1 10.6 99.5

toluene 3.5 33.2 95.1

C8 7.2 22.8 84.8
C9 5.1 11.2 70

Table 5

Takeoff of Aromatic hydrocarbon

Degree of extraction, wt. %
saturated content, wt. %
Yield of
Temperature hydrocarbons
distillate,
in boiler, °C with aromatic
wt. %
distillate, in distillate in bottoms hydrocarbons benzene
wt. % (total)

in azeotropic distillation
133 1.3 21.1 9.2 95.7 99.9 99.3

140 3.9 53.9 26.2 97.4 98.9 93.9

156 8.3 78.6 49 98.7 95.7 75.7

163 13.1 91.9 62.5 99.5 91.3 50.7

180 16.9 96.9 67 99.8 87.7 32.1

in extractive-azeotropic distillation
125 1 18.7 5.7 95.6 99.9 99.9

160 2.9 48.6 11.5 97.2 99.6 98

180 4.8 72.5 19.8 98.4 99 94.2

Experiments 3 and 4 are intermediate, conducted to sufficiently completely extract benzene and obtain
extracts containing a minimum of 75-80 wt. % aromatic hydrocarbons.
The saturated hydrocarbons remaining in the extract should primarily be represented by C 6-C 7 paraffins
and naphthenes. For this reason, it was hypothesized that the C 8 -C 9 aromatic hydrocarbon fractions separated

219
from the extracts by distillation would be suitable for production of o- and p-xylenes and an aromatic solvent of
the Nefras AR-120/200 type without further treatment.
Raffinate containing almost no aromatic hydrocarbons was obtained in the conditions in Experiment 1,
but the yield was very low, and only 35 wt. % of the saturated hydrocarbons contained in the reformate passed
into it (Table 4).
Raffinate that satisfied the requirements of the Euro-4 program for automotive gasolines both with respect
to the total aromatic hydrocarbon content and with respect to the benzene content (with a twofold margin) was
obtained in the conditions of Experiment 2. The yield of raffinate, in consideration of the high aromatic
hydrocarbon content in the reformate, was relatively high. Only ~5 wt. % of the saturated hydrocarbons from the
potential content in the feedstock passed into the extract.
Capillary gas-liquid chromatography showed that the saturated hydrocarbons in the extract are distributed
by groups as follows, wt. %: 0.7 C 4 ; 10.6 C 5; 40.3 C 6 ; 33.1 C 7; 6.7 C 8 ; 8.6 C 9. Approximately 85 wt. % of
saturated hydrocarbon contaminants are thus represented by components with boiling points below 100°C.
In consideration of the predominance of low-boiling saturated hydrocarbon contaminants in the extract,
we attempted to remove them by azeotropic distillation of the extract phase obtained in Experiment 2 with ethanol.
Ethanol was used as a promising high-octane gasoline additive in place of methyl tert-butyl ether [18].
The advantage of using high-octane alcohols as azeotrope-forming components in treatment of benzene
and its homologs, as shown previously in [19], is that they can not be regenerated, but the distillate obtained can
be used as a component of gasoline. Consumption of ethanol in extract was 5 wt. %, or 83 wt. % in saturated
hydrocarbon contaminants.
Azeotropic distillation was conducted in a periodically operating tower with efficiency corresponding
to 15 theoretical plates. The degree of extraction of toluene at the end of the experiment was 99.1 wt. %. However,
in addition to high-boiling saturated hydrocarbon contaminants, more than half of the benzene contained in the
extract was also distilled off (Table 5).
Extractive-azeotropic distillation was conducted to decrease losses of benzene. Ethanol was added to the
extract phase in the ratio of 0.05:1 (wt.) and the tower was additionally sprayed with sulfolane in a ratio to the
extract of 0.55:1.
In extractive-azeotropic distillation with a high mass ratio of sulfolane and ethanol to
extract, 0.7:1 and 0.08:1, bottoms were obtained with a yield of 94.5 wt. % and total aromatic hydrocarbon content
of 99.7 wt. %. The degree of extraction of benzene, toluene, and C 8+ aromatic hydrocarbons was 94, 99.9 and
100 wt. % in this case.
The total mass ratio in the stages of extraction and extractive-azeotropic distillation was 1.88:1 for sulfolane
and feedstock and 0.032:1 for ethanol and feedstock. There were no recirculating streams in the proposed
combined process.
The degree of extraction of benzene, toluene, and C 8 and C 9 aromatic hydrocarbons in the combined
method attained 89.3, 76.9, 69, and 24 wt. %, respectively. After combining the raffinate from the extraction stage
with the distillate from the extractive-azeotropic distillation tower, gasoline component was obtained with a yield
of 65.4 wt. % in feedstock. its composition, wt. %, was: 27.7 % hydrocarbons, including 1.07% benzene;
67.4% saturated hydrocarbons; 4.9% ethanol.

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